Novel polyimidamide resin



NOV 1970 MlNEO NAKANO L NOVEL POLYIMIDAMIDE RESIN Filed Sept. 11, 1968 2' Shee ts-Sheet 1 0 I 1 l I I a 1 4000 3000 2000 /000 I600 /400 /200 /000 000 650' W4VE NUMBER 0M" INVENTORS fill/v80 fink/9N0 ATTORNEYS atettt l 3,541,038 Patented Nov. 17, 1970 3,541,038 NOVEL POLYIMIDAMIDE RESIN Mineo Nakano and Takeshi Koyama, Hitachi-shi, Japan, assignors to Hitachi Chemical Company, Ltd., Tokyo, Japan, a corporation of Japan Continuation-impart of application Ser. No. 537,388, Mar. 25, 1966. This application Sept. 11, 1968, Ser. No. 759,130 Claims priority, application Japan, Mar. 30, 1965, 40/ 18,014 Int. Cl. C08g /32 US. Cl. 26030.6 10 Claims ABSTRACT OF THE DISCLOSURE This is a continuation-in-part of application Ser. No. 537,388, filed Mar. 25, 1966, now abandoned.

The present invention relates to a novel polyimidamide resin. More particularly, this invention is concerned with a novel, high molecular weight polyimidamide resin having high thermal resistance and electric insulation prepared by subjecting a tribasic acid anhydride and a diisoresistance and electric insulation. Another object of the present invention is to provide an electric insulator obtained by applying the novel polyimidamide resin as such or in the form of a solution in an organic solvent to an electroconductor.

The other objects and advantages of the present invention will be apparent from the following description.

The novel polyimidamide resin of the present invention is prepared by subjecting substantially equimolar amounts of a tribasic acid anhydride and a diisocyanate compound to polycondensation at a temperature of about 60 to 150 C. in the presence of an inert solvent, while removing the formed carbon dioxide from the reaction system. Thus, the novel polyimidamide resin can be prepared in one step without requiring any additional complex purification as in conventional methods and without causing gelation. Further, the time required for the condensation may be short and is ordinarily within 2 to 4 hrs.

The polyimidamide resin of the present invention has substantially no terminal isocyanate groups unlike the resin of US. Pat. No. 3,314,923.

The present polyimidamide resin is excellent in thermal resistance and electric insulation because of its having no terminal isocyanate groups unlike the resin of US. Pat. No. 3,314,923, and not only is it usable, either as such or in the form of a solution in an organic solvent, as coil-impregnation varnishes or electric insulation varnishes, such as wire enamels and varnish cloths, but its solution can also give films excellent in mechanical strength.

Tribasic acid anhydrides which may be used in the present invention include aromatic, alicyclic and aliphatic tribasic acid anhydrides, such, for example, as trimellitic anhydride, hemimellitic anhydride and aconitic anhydride.

cyanate compound in substantially equimolar amounts to Diisocyahate Compounds Which y be used in the pols/condensation present invention include aromatic diisocyanate com- US. Pat. No. 3,314,923 to Muller et a1. discloses the p such as p y oxide diisocyanate, p y production of polyisocyanates containing imide groups methane dllsocyahate, tolylehe dllsocyahate, phehylelle by condensing a monomeric polyisocyanate with a trilsocyahate, y y diisocyanate, p y Sulfohe diisobasic acid anhydride at a temperature of at least about y naphthalene dllsocyanatfi and the like; alicyclic 50 c. in a proportion of at least 1.1 equivalents of the dnsocyanate compounds, Such as cyclohexane diisocya- NCO group per functional group f h t ib i id nate, cyclopentane dnsocyanate and the like; and a1ianhydride. However, since the monomeric polyisocyanate Phatic dllsocyahate Compounds, Such as hexamethylehe is used in stoichiometric excess, the reaction tends to form diisocyanate, tetramethylehe diisocyanate and t likea gel, and the produced resin has terminal isocyanate P y Oxide dllsocyahate 15 most Preferablegroups. Therefore, said resin is not useful as an insulating The shperlorlty 0f P Y OXidfi dllsocyanate 10 Other material for electroconductors though may be used as dllsocyahates 15 clear from Table 1 and FIG 2 0f the adhesives or as auxiliary agents for rubbers, attached drawings. FIG. 2 shows the weight reduction, as

An object of the present invention is to provide a novel, measured y thefmohalahce analysis, of Various P 3- high molecular Weight polyimidamide resin having subimidamide resins having a molar ratio of the diisocyanate stantially no terminal isocyanate groups and high thermal to trimellitic anhydride of 1.06.

TABLE 1 Tri- Bakin conditions S mellitie Diphenyl- Diphenyl- Non- 1Z0 mm anhymethane diether divolatile Viscosity Drawing Final Con- Film dnde, isocyanate, lsoeyanate, matter, at 30 0., Temp., rate, Workoutside ductor thick- Sample No. mole mole mole percent poise 1 Sp./c. C. m./min. ability diameter diameter ness Flexibility Degradation at 200 0. Degradation at 250 0. Thermal shock resistance at Normal state for 24 hrs. for 24 hrs. 350 C. for 1 hr. Sample No. x1 x2 x3 x4 x1 x2 x3 x4 x1 x2 x3 x4 x1 x2 x3 x4 0 0 0 0 0 0 0 0 o 0 0 0 0 0 0 0 1 0 0 0 0 0 0 o 0 (1)1 0 0 0 1 0 0 o 0 0 0 0 0 0 0 0 2)2 (2)2 0 0 0 0 0 0 0 0 0 0 0 0 0 0 1 0 0 0 2 0 0 0 0 0 0 0 0 o 0 0 0 0 o 0 0 0 o 0 0 0 0 0 0 Footnotes at end of table.

TABLE 1C011tinued Breakdown Thermoplastic Abrasion resistance 600 g., voltage Chemical resistance flow at 350 0. times- Twist for- 6 hrs., resistance, Kv./0.1 NaOH, Toluene- Sample No. weight, 700 g. Max Min. x times Kv. mm. Benzene H2804 ethanol OK 2, 270 137 1, 053 81 11. 1 l3. 9 7H 6H 7H 7H 1 OK 4, 905 779 2, 352 82 11. 4 14. 2 7H 6H 7H 7H 0 K 2, 462 742 1, 728 79 10. 9 13. 6 7H 6H 7H 7H 0 K 6 337 472 74 12. 8 17. 3 6H 7H 6H 7H 2 OK 1, 259 203 639 81 12.4 15. 9 6H 7H 6H 7H 7' 324 502 83 13. 9 17. 4 6H 6H 6H 7H 1 Good. 2 Peeled.

No'rE.'lhe polymer used was prepared by charging 0.100 mole of trimellitic anhydride in 130 g. of N-methyl-2-pyrrolidone and then 0.106 mole of a diisocyanate with stirring into a gig) mixture at said temperature for 30 min., further elevating As the inert solvents, there may be used dimethylacetamide, dimethylform-amide, N-methyl-Z-pyrrolidone, hexamethyl phosphoramide and the like, among which N-methyl-Z-pyrrolidone is most preferred.

Although the tribasic acid anhydride and the diisocyanate compound are condensed by heating them in the presence of an inert solvent, the carbon dioxide formed during the reaction should be removed as much as possible from the reaction system, because when the carbon dioxide bubbles are left unremoved, undesirable effects are brought about in view of the characteristics of the resulting resin when used for the desired application. The time for the condensation reaction of the tribasic acid anhydride and the diisocyanate compound is not particularly critical or restricted so far as a required and sufficient time is employed to complete the reaction. The condensation reaction temperature is within the range of from 60 to 150 C.

In the present invention, the amount of the tribasic acid anhydride and that of the diisocyanate compound must be substantially equimolar to each other, preferably in a proportion of 1.00 to 1.06 moles of the diisocyanate compound per mole of the tribasic acid anhydride. When the diisocyanate compound is used in an amount of at least 1.1 moles per mole of the tribasic acid anhydride, the reaction becomes very diflicult owing to a rapid increase in viscosity or to gelation, which requires addition of a further solvent, whereby only a low resin concentration varnish is produced which is very unsuitable for the formation of an enameled wire. Further, when the diisocyanate compound is used in an amount of at least 1.1 moles per mole of the tribasic anhydride, the produced varnish is much inferior to the present resin varnish in storage stability, workability in baking enameled wire and the characteristics of enameled wire.

The following examples further illustrate the present invention.

EXAMPLE 1 To a 500 ml., three-necked flask equipped with a stirrer, a thermometer and a cooling pipe were added 50 g. of diphenylmethane diisocyanate and 100 ml. of dimethylacetamide. To the flask was further added a solution of 37 g. of trimellitic anhydride (the molar ratio of the diisocyanate to the anhydride is 1.04) in 100 ml. of dimethylacetamide. When the temperature was elevated to between 80 C. and 100 C., a vigorous reaction occured and the generation of carbon dioxide was observed.

The temperature was further elevated, and at a temperature of 120 C. to 150 C., stirring was effected for about one hour, whereby the color of the solution changed from colorless to yellow and further to red, and the viscosity of the solution greatly increased. The heating was further continued for about two hours, and then the reaction was terminated. The resulting polyimidamide resin has an intrinsic viscosity of 0.92 as measured in dimethylformamide at 25 C. The melting point of the resin was above 320 C., and the Weight loss thereof due to heating in air at 250 C. for three days was 1%.

The infra-red absorption spectrum of the resin is shown 300 ml., tour-necked flask with a calcium chloride-packed tube, thereafter elevating the temperature to 60 0., stirring the temperature to 120-130 0., and effecting the reaction at said temperature for about in FIG. 1. In the infra-red absorption spectrum, absorption due to amide linkages is seen at 3300 cmf 1660 cm.* and 1530 cmf and the characteristic absorption of the cyclic imide carbonyl radical is observed at 1776 61111 and 721 cmf In view of the above fact, it is confirmed that the resin produced is a polyimidamide resin. The resin solution obtained was poured in a thickness of 0.5 mm. onto a plate and then heated at 120 C. and 150 C. each for about 30 min. to obtain a tough film.

EXAMPLE 2 To a 500 ml., four-necked flask equipped with a stirrer, a nitrogen gas-introducing pipe, a thermometer and a cooling pipe were added 50 g. of diphenyl oxide diisocyanate and 100 ml. of dimethylacetamide. To the flask was further added at one time a solution of 38 g. of trimellitic anhydride (the molar ratio of the diisocyanate to the anhydride is 1.00) in 100 ml. of dimethylacetamide. When the temperature was elevated to about 90 C., the generation of carbon dioxide was observed, and the color of the solution became yellow. The solution was further heated at 150 C. for 1 to 2 hrs., whereby the color of the solution became deep red and the viscosity thereof greatly increased. The heating was continued for about 3 hrs. and the reaction was then terminated.

The resulting resin had an intrinsic viscosity of 0.45 as measured in dimethylformamide at C. The resin solution obtained was poured in a thickness of 0.5 ,mm. onto a plate and then heated at 120 C. and 150 C. each for about min. to obtain a tough film.

EXAMPLE 3 To a 500 ml., four-necked flask equipped with a stirrer, a nitrogen gas-introducing pipe, a thermometer and a cooling pipe were aded g. of diphenylmethane diisocyanate and 100 ml. of dimethylacetamide. To the flask was further added a solution of 37 g. of trimellitic anhydride (the molar ratio of the diisocyanate to the anhydride is 1.04) in 100 ml. of dimethylacetamide. When the flask was heated to C.- C., a vigorous de-carbon dioxidation reaction was caused and the generation of carbon dioxide was observed.

The temperature was further elevated, and at C.- C., stirring was effected for about 3 hrs., whereby the color of the solution changed from colorless to yellow and further to red, and the viscosity thereof greatly increased. At this time, the reaction was ceased.

The resulting polyimidamide resin was diluted with dimethylacetamide to a non-volatile content of 20% and a viscosity of 10 poises (at 25 0., BL type). Thereafter, the resin was applied to a 1.0 mm. diameter, soft copper wire and baked thereon under the following conditions to form a 0.035 mm. thick film:

Number of times of application: 7 Drawing rate: 5 m./min. Baking temperature of funnel:

At top of funnel: 400 C. At center of funnel: 250 C. At entrance of funnel: 100 C.

The characteristics of the thus obtained insulated electric wire were as follows: Winding test (the coated wire was wound around a wire having the same diameter) (after heating at 220 C. for 6 hrs.) according to Japanese Industrial Standard C-3203-1957 was good; thermal 6 EXAMPLE The three varnishes obtained in Example 6 were applied to 1.0 mm. diameter, soft copper wire and baked thereon as in Example 5 to obtain the results shown in Tables 2 and 3.

shock resistance (at 250 C. for 1 hr., the coated wire was 5 wound around a wire having the same diameter) was TABLE 2 extremely high; abrasion resistance was 218 times (load: Varnish No. 700 g.); breakdown voltage was 8.9 kv. (after heating 1 2 3 at 220 C. for 24 hrs.) and resistance to monochloro-di- M 1 t, id t t h d d 0 oar re 10 0 iisocyana e can y ri e 1.15 1.12 1. 6 fluoromethane was very hlgh' Irtesin eonttgrg prcent 25.0 30. 3

iscosi y a poises 9 3. 5 7 EXAMPLE 4 Number of times of application 9 8 Drawing rate (m./mi.n.) in baking and appearance:

Into a 3 l1ter, four-necked flask equipped with a cal- 7 g cium chloride-packed tube were charged 384 g. (2.00 moles) of trimellitic anhydride and 2 kg. of N-methyl- 2-pyrrolidone, and 530 g. (2.12 moles) of diphenylmethane diisocyanate was then stirred into the flask. The resulting mixture was heated, while being stirred, to a temperature of 120 C. to 130 C., during which a violent de-carbon dioxidation reaction took place. After 1.5 hrs.

TABLE 3 Varnish N0.

Drawing rate, m./min 7.5 8.5 7.5 8.5 9.5 7.5 9.5 11.5 13.5 Thickness oifilm, mm 0.027 0. 03s 0. 038 0.039 0.039 0.038 0.038 0.039 0. 040 Flexibility:

Normal state, x1 0 O 0 0 0 0 0 0 0 After stretching:

x1 (5)5 (5)5 (5)5 (5)5 (5)5 (5)5 (5)5 0 0 (5) 5 (3) 3 (5) 5 (5) 5 (1) 1 (5) 5 0 0 0 o 0 (2)3 0 0 0 0 0 0 0 0 1 0 0 o 0 0 0 0 2 2 1 1 1 0 0 0 0 0 1 o 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 Abrasion resistance, times 379 464 384 676 481 310 375 290 293 Twist resistance, times 67 67 66 70 67 64 72 72 83 Thermoplastic flow, 350 0., 6 hrs A x o A A o o o o Breakdown voltage,kv 13.8 12.5 11.3 12.0 11.5 14.9 15.2 16.2 16.0 Chemical resistance:

Benzene 7H 7H 7H 7H 6H 7H 7H 7H 7H Caustic soda. 6H 6H 6H 6H 6H 7H 7H 6H 6H Sulfuric acid- 6H 6H 6H 6H 6H 7H 7H 7H 7H Toluene-ethanol- 6H 6H 7H 7H 7H 7H 7H 7H 7H l Peeled.

NOTES:

1. The flexibility and the thermal shock resistance are expressed by the number of coils inwhich pin holes were formed when five sample coils were sublected to test. The figure in parentheses refers to the number of coils having cracks confirmed with the naked eye.

2. The thermoplastic flow was determined by elevating the temperature at a rate of 300 C./2 hrs. and maintaining at 350 C. for 6 hrs. 0 refers to OK for 6 hrs., A to flow within 6 hrs. at 350 C. and x to flow during the temperature elevation.

at said temperature, the mixture began to show a viscosity. In about 4 hrs. from this point, the viscosity of the reaction product became substantially constant and the generating rate of carbon dioxide became very small. This point was decided to be the end of the reaction. The resulting resin solution had a Gardner viscosity of 70 poises at 25 C. and a resin content of 31%.

For comparison, the same procedure was repeated by use of molar ratios of the diisocyanate to the anhydride of 1.12 and 1.15. When the ratio was 1.15, gelation was caused, and when the ratio was 1.12, gelation was not caused but the viscosity increase during reaction was very rapid, and hence the progress of reaction became very difficult.

Further, the viscosity of the varnish obtained by use of a molar ratio of the diisocyanate to the anhydride of 1.06 did not change at all with the lapse of time at both room temperature and C., while the viscosities of the varnishes obtained by use of the other ratios decreased rapidly with the lapse of time at both of said temperatures.

As seen from Table 2, when the ratio is 1.15, the drawing rate must be lower than 8 m./min. to obtain good appearance of baked enamled wire, while when the ratio is 1.06, a drawing rate of 15 m./min. can be used to obtain good appearance. Further, it should be noted that when the ratio is 1.06 a varnish having a high resin content-is obtained, and hence 8 times of application is suflicient as compared with 9 times of application of the other varnishes.

Table 3 clearly shows that Varnish No. 3 is superior to the others in flexibility, particularly after heat-degradation, and thermoplastic flow.

We claim:

1. A high molecular weight polyimidamide resin having high thermal resistance and electric insulation prepared by subjecting a tribasic acid anhydride and 1.00 to 1.06 moles, per mole of the anhydride, of an organic diisocyanate compound to polycondensation at a temperature of about 60 C. to C. in the presence of an inert solvent.

2. A high molecular weight polyimidamide resin according to claim 1, wherein the tribasic acid anhydride is trimellitic anhydride.

3. A high molecular weight polyimidamide resin according to claim 1, wherein the organic diisocyanate compound is diphenyl oxide diisocyanate.

4. A high molecular weight polyimidamide resin according to claim 1, wherein the organic diisocyanate compound is diphenylmethane diisocyanate.

'5. A high molecular weight polyimidamide resin according to claim 1, wherein the inert solvent is Nqmethyl- 2-pyrrolidone.

6. An electroconductor having a polyimidamide insulating resin coated thereon, said resin being prepared by subjecting a tribasic acid anhydride and 1.00 to 1.06 moles, per mole of the anhydride, of an organic diisocyanate compound to polycondensation at a temperature of about 60 C. to 150 C. in the presence of an inert solvent.

7. An electroconductor having an insulating polyimidamide resin solution coated thereon, said resin solution being prepared by subjecting a tribasic acid anhydride and 1.00 to 1.06 moles, per mole of the anhydride, of an organic diisocyanate compound to polycondensation at a temperature of about 60 C. to 150 C. in the presence of an inert solvent, and then dissolving the resulting high molecular weight resin in an organic solvent.

8. A coating composition comprising a polyimidamide resin dissolved in an organic solvent, said polyimidamide resin being prepared by subjecting a tribasic acid an- 8 hydride and 1.00 to 1.06- moles, per mole of the anhydride, of an organic diisocyanate compound to polycondensation at a temperature of about C. to C. in the presence of an inert solvent.

9. A coating composition in accordance "with claim 8, wherein said organic solvent is selected from the group consisting of dimethylacetamide, dimethylformamide, N- methyl-Z-pyrrolidone, hexamethyl phosphoramide and mixtures thereof.

10. A high molecular weight polyimidamide resin having high thermal resistance and electric insulation prepared by subjecting equimolar amounts of a tribasic acid anhydride and an organic diisocyanate compound to polycondensation at a temperature of about 60 C. to 150 C. in the presence of an inert solvent.

References Cited UNITED STATES PATENTS 3,260,691 7/1966 Lavin et al. 260--30.2 3,300,420 1/196'7 Frey 260-25 3,314,923 4/ 1967 Muller et al 260-78 3,347,828 10/ 1967 Stephens et a1 26047 r WILLIAM H. SHORT, Primary Examiner L. L. LEE, Assistant Examiner US. Cl. X.R.

ll7-l28.4, 161, 232; 260-32.4, 32.6, 47, 77.5 

